Resin process



May 9, 1950 J. D. GARBER ET AL RESIN PROCESS Filed April l'',v 1946 I ll Il SQQ mrwm. ruig NLQ NQ .l OU kk QM Qu@ t W1 l M2 S. M

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lll WUQOLM Q SND QOL m Sfr@ S Patented May 9, 1950 UNITED STATES EATENT OFFICE RESIN PROCESS- Application April'A 17, 1946, Serial No. 662,693

Claims. (Cl. 260-853') This invention relates to ol'e'nic polymers, relates particularly to the production oflight colored polymeric resins, and relates especially to means for reducing to the lowest possible value color-producing iron contaminants.

It has been found possible toA produce an extremely Valuable synthetic resin from a mixture of mono-olefins and multi-olefins iin which mixture there may be present from 30 per cen-t to 80 per cent of a multi-olefin such butadiene or other multi-olefins having from 4 to I4 carbon atoms per molecule With the remainderconsisting of a mono olen having 5 to about 2O carbon atoms or a normal olefin having from 3- to'- 20 carbon atoms, by the application"V to the mixture of a Friedel-Crafts catalyst at temperatures ranging from about- +110 to 30 C; to' produce a resin which is not an elastomer but is a hard, solid, hydrocarbon -soluble substance having many of the characteristics of the natural varnish gums and resins. However', diiculty has been encountered in the production oi these resins because ot the tendencyv of theA resin to assu-me a more or less deep yellow to brown color Which reduces its value for thev making ot clear varnish compositions.

It is now found that if the resin, in solution in light solvent vis carefully washed with water orwith the water solutions of moderately alkaline substances such as soda followed by a thorough water wash and is then dried and the solvent flashed out in the shortest possibletime, with aY minimum of contact with iron-containing structures, a resin can be` obtained which is nearly Water White.

For this purpose, the resin solution is delivered from the reactor to a Washl tank. Where it is washed preferably with water to' removeA as completely as possible all traces of aluminum and iron, settled to remove as muc-h as possible of the insoluble cross-linked material' and then passed through a double pipeA heat exchanger in which the resin solution isin contact'. for as short a time as possible with a non-ferrous tube struc-ture containing less than 5V per cent iron impurity; and the emergenty molten resinV isc collectetl andy further puried in a: similar non- 2 ferrous drum receiver. 'The preferred material for the tube and receiver is the copper nickel alloy known asl MonelWmetaL By this procedure the amount off iron in the resin can be kept below amounts as low as 5 to 2'5 parts per million and at these values the resin is transparent and ractical-ly water White.

'Ilius the invention polymerizes a diole-n such asi butadiene in proportions from 30% tol 80% with' a mono olefin such as diisobutyl'ene in pro'- portions from to 20% at temperatures within the range between +10 and -30' C. by the appli'cation thereto, in the presence of a di-luent such as liquid propanev or butane, if desired, of a Friedel-Crafts catalyst such asaluminum chloride in. solution in ethyl or methyl chloride or' AlB'rs in solution in hydrocarbons such as butane, hexane or the like to"r yield a solution of resin` unpolymeri-zed diolen, mono-olefin', catalyst solvent and dil-nent. After the polymerizati'onv reactien has beenP carried' to the desired stage, the reaction` mixture is Washed repeatedly with- Water or4 with a very mild alkali such as a sodium bicarbonate solution: and then, with further repeated washingsof Water, until a condition of neutrality is obtained; that is, a pH of about 7i. The Washed solution is then settled to remove the gel and the cross-linked, insoluble material', and isl then passed throughl a heat exchanger and flash volatilization device made from a material substantially free from. iron, preferably Monel metal (copper nickel alloy), or nichrome (nichel chromium alloy), or glass lined" equipment the length of time or contact with the' hot metal being sharply limited to four minutes' or less', the molten liquid resin being coil'ected'. in: a similar non-ferrous receiver, where it is further steamestripped by a current of superheate'd live steam and a heating coil, and the molten resin is then piped to storage packages. Other objects' and: details of theI inventionI will be apparent from theiollowin'gk description when read in connection with the accompanying drawing, wherein' the' single figure is diagrammatic representationr ot apparatus' and'. process steps according to the invention;

The raw material for the present' inventionE is a low temperature resin prepared from a multiolen and a mono-olen. The preferred multiolen is butadiene, but any substituted butadiene or any multi-olen having more than one Vdouble linkage is useable; including such substances as isoprene, piperylene, the several dimethyl butadienes, dimethallyl, myrcene, divinyl benzene, allo-ocymene, and the like, any multi-olenic substance having two or more double linkages per molecule, and from 4 to 14 carbon atoms being useful. This material is copolymerized with a mono olen such as propylene, or normal butylene, all of the pentenes, hexenes, heptenes, octenes, nonenes, and the like, up to about 20 carbon atoms being equally useful. That is, all of the normal mono olei'ins having from 3 to 20 carbon atoms inclusive are useful and all of the secondary and tertiary mono olens from 5 to 20 carbon atoms, similarly being equally useful (isobutylene is not useable in this reaction since its high polymerization reactivity results in the polymerization of the isobutylene with a relatively very small amount of the multi olefin, yielding a wholly diierent, rubbery, type of substance, or a thick oil not a hard resin).

The preferred mixture is from 30% to 80% of the multi-olefin, preferably butadiene because of its cheapness and availability, with from 70% to 20% of diisobutylene, also because of its cheapness and availability. These materials are mixed, diluted with an appropriate amount of a diluent such as liquid propane and polymerized by the addition of the appropriate catalyst.

Referring to the drawing, the butadiene is stored in tank I to which it is delivered through a pipe 2 by a pump 3, the suction of which is drawn from some such supply as a tank car. Simultaneously, the dimer is stored in a tank 4 after receipt from the renery or other convenient source. Preparatory to use, the butadiene is passed through a calcium chloride dryer 5 and the dimer through a calcium chloride dryer 6. Both dryers discharge through a pipe 'I into the reactor 8. The reactor contains a propeller stirrer 9 which is driven by an appropriate motor, (not shown). Simultaneously, a supply of ethyl chloride is stored in the container Il, to which it likewise is delivered from tank cars or other source of supply. The ethyl chloride likewise is passed through a calcium chloride dryer I2 to one or the other of mixing drums I4. From the mixing drums I4, the ethyl chloride is circulated through an aluminum chloride dis- -solver I5 by a pump I6 until a suiciently strong solution of aluminum chloride is obtained in the drums I4.

In the meantime, an appropriate amount of liquid propane is delivered to the reactor 8 through a pipe line II. The propane is volatilized by the warmth of the butadiene and dimer in the reactor 8 and passes upward through the pipe I8 to a reflux condenser I9, cooled with liquid ethane delivered through the supply pipe 2 I. The reflux of cold propane flows downward through the pipe 22, back into the reactor 8. This reilux cooling is continued until the material is brought down to the desired temperature which is determined by the mixed boiling point of the contents of the reactor, the amount of propane present being brought to a value such that the mixed boiling point is at the desired temperature. It may be noted that while liquid propane is in some ways preferable, gaseous propane is useable, since after introduction, it is cooled in the reux condenser I9 and delivered as liquid through the pipe 22 to the reactor 8. When the desired temperature is reached, the catalyst is delivered by the pump 23 through pipe 24 to the reactor 8 in the form of a fine, high-pressure jet which is very rapidly stirred into the olefin-containing mixture. The reaction proceeds promptly to yield the desired polymer resin. The rate of reaction is to a considerable extent determined by the rate of catalyst delivery, and the rate of delivery is preferably kept at a comparatively low value to avoid undue temperature rise in the reactor; that is, with a reactor containing 550 pounds of butadiene and 450 pounds of dimer dissolved in approximately 700 pounds of propane, approximately '75 gallons of a 3 aluminum chloride solution in ethyl chloride are required for conversion of approximately 75% of the olenic material; and this amount of catalyst is delivered over a time interval of approximately 1 to 2 hours. When the reaction has reached the desired stage, a supply of light naphtha from the storage tank 25 is delivered by a pump 26 through a calcium chloride dryer 2'I to the reactor 8 where it is well stirred in by the stirrer 9. When a solution of the desired concentration has been obtained by this means, a valve in the pipe 2l is opened and the pump 28 drains the solution of polymer from the reactor 9 and delivers it to a wash tank 29 equipped with a stirrer 3|. Simultaneously, water from a tank 32 is delivered through pipe 33 to the washer 29. The wash water is at a temperature considerably above the temperature of the polymerizate solution, and considerably above the boiling point of the ethyl chloride, the unreacted butadiene, and the propane. Accordingly, these components of the reaction mixture are volatilized out and discharged through an outlet pipe from the washer 29, whereafter, they may be sent to a flare for burning or may be recovered, recycled and reused in subsequent polymerizations.

The pump 34 serves to circulate the wash water and polymer solution to obtain as complete a washing as possible; at intervals the stirrer 3! is allowed to stop and the wash water or wash solution is drained off and replaced by fresh water; to avoid troublesome emulsions the wash water is preferably left at 13D-150 F. When the material has been washed to the desired Stage and has reached a condition of neutrality, as is shown by tests of the wash water; from 3 to 1l successive washings, each using a volume of water approximately equal to the volume of light naphtha solution being required. The polymer solution is then transferred by the pump 34 to a settling drum 35 in which the insoluble crosslinked resin settles out. The clear upper portion is then decanted through a pipe 3B to a pump 3'I by which it is delivered through a non-ferrous steam jacketed pipe system 38.

This system consists of an inner pipe made of a non-ferrous material such as Monel metal or nichrome or copper, or the like, or is glass lined and is surrounded by a jacket of high pressure steam at from to 250 pounds per square inch pressure. The polymer solution delivered by the pump 3'I into the inner pipe is rapidly heated to a temperature above the melting point of the resin, usually far enough above the melting point to leave the resin in a relatively fluid form, and, accordingly, the rate of passage is quite rapid. To facilitate complete removal of solvents from the resin, a stream of superheated steam is introduced into the coil at a point where the temperature of the resin mass is above 212 F.

(usually about midway fthelength'- f thel coil; this point being chosen in order" that the temperature may be above the condensation point of Water.

The steam serves as a stripping agent to carry forward and away as much as possible of the light naphtha. Instead of steam, such substances as nitrogen, carbon dioxide, clean ue gas, or other inert gaseous material which shows a low solubility in the polymer may be used.A

A one-inch internal diameter p'ipe, con` structed of Monel metal, having an overall length of feet will handle approximately 1.6 gallons of polymer solution per minute when the solution contains %*v of resin. The ob-Y tainable flow rates and the characteristics of the material are well shown in the following table:

The coil was thoroughly washed with diisobutylene between each of the above runs to avoid contamination. The resin produced wasA a, s butadiene 15-dimer type resin which had a melting point of 91 C., and when finished in glass had the following properties: varnish color=l1, ash=0.02% and iron=0.0004%. Thus the polymer solution must be fed to the equipment at a rate of 0.6 to 1.5 gal/min. in equipment of the stated design in order to maintain product quality.

It may be noted that even the best of Monel and nichrome alloys will contain from 2 to 6 or 7% iron, and some of this iron is unavoidably absorbed by the resin. However, if the time of passage of the hot resin through the heater tube is less than four or ve minutes, the amount of iron picked up by the hot resin is less than about 10 parts per million, which does not cause a serious amount of discoloration. A

From the exit end of the Monel pipe, the resin is discharged to a disengagng drum 39 in which the molten resin is separated from the nonpolymerized material at a temperature of ap-V proximately 280 F. From the drum 39 any residual, unpclymerized dimer and light naphtha added to the polymerizer to dilute the solution are driven off through the pipe 4I to the condenser 42. Simultaneously, the temperature in the receiver 39 is maintained by a steam coil 43 and by open steam from a distributor 44. In the condenser 42, the water, the dimer, and the added naphtha are condensed and delivered to a receiver 45. The water is drained out through a pipe 48 and sent to the sewer, and the naphtha, with small amounts of dimer, and so on, is drained out through the pipe 49 and returned by the pump 5| to the naphtha storage.

In the recovery of this copolymer resin it is essential that a relatively narrow range of conrditions of temperature and throughput through the coil must be obtained andth'ese values are f." time is long enough and temperature high enough to free the Vsolution from volatile components, and thejrate of flow is fast enough and the temperature low enough to prevent the contamination with iron to an extent sucient to is' discolor the resin. In the embodiment herein,

as above described, a Monel metal coil having a diameter of 1 inch and a length of 40 feet was used, surrounded` with a steam jacket at a pressure of 105 lbs/sq. in.

In the device and lprocess above described, a substantial amount of light naphtha diluent is delivered directly to the polymerizer, but with the reflux condenser attached, the temperature does not rise above the boiling point of the lower-boiling components, and, accordingly', a very uid solution is delivered. by the pump 28 to the washer 3|. This method of operation is, however', not necessary. Instead, the pipe I8 leading to the reflux condenser may be closed by a valve before the naphtha is introduced, and the naphtha may be warmed substantially before being introduced. AUnder these circumstances, the light volatiles may be discharged through a pipe 20 leading from the top of the reactor to a recovery and recycle system (not shown) by which the butadiene, the methyl chloride, and the propane are separated by a fractional distillation and stored in proper storage tanks for reuse. By this procedure, a somewhat heavier, more viscous solution is delivered by the pump 28A to the washer 29, and substantially no light volatiles are disengaged in the washer. This procedure has some' points of value in that it permits of recovery and reuse of many of the components; on the other hand, the cost of equipment and power for the fractional distillation may, Vin some instances, amount to more than the value of the recovered materials.

It is of interest to note the surprising power of iron to degrade the color of this hydrocarbon type resin, The resin is Wholly free from acid substituents and should be wholly non-corrosive. Nevertheless, at high temperatures, its attraction for traces of iron is phenomenally and uneipectedly high, to such. an extent that it can not be processed readily in iron equipment, even stainless steel, vvithout a serious or fatal contamination by iron which, in amounts above about vim parts per million, yields a deep yellow color, and,

(fhf, sible to bring the resin solution to a closely neucritical; thus, if the rate of flow of the resin r tral condition, and then removes the solvent by a heat treatment in the absence of ferrous structures to maintain as low an iron content as pos-v sible.

EXAMPLE I A series of polymerizations 'were conducted, as above outlined, and successive portions of the various .polymerizations Werprocess'ed in the 5 Monel metal 'coil abo'v'e described.

The results are summarized in the following concept herein disclosed and it is therefore detable: sired that only such limitations be imposed on Table No. I-Test runs on flash coil, resin plant [Equipment: 40 ft. of 1" Manel pipe, steam Jacketed. Steam injection at middle of coil. Steam pressure: 114-117 P. S. I. G.]

Steam to Coil Coil Temp., F. Heat Transfer Vapor Vel., Ft./Sec.

Coil Feed Batch Test, GRlat/,I Mols/Mol. Solv. i Basis E rtxi rniiserlilt No' 11E-un 'Sol'u- I Lb /H In] t lihfdle O t] t gaat? Seam 1" Coil 12" 3" gaglng Drum o. r. e e ore u e ea ontion HIiln Steam Pickup su'mp Outlet Drum Drum Feed Feed non (d) (d) (a) (b) (C) 73-74-75. 1 0.056 98 75 75 68 216 290 4, 300 141 1.1 No Observation.

2 0. 173 98 24.3 24. 6 68 215 237 1l, 000 67, 000 136 1.0 Do. 3 1. 58 9S 2.6 3.0 68 185 237 101,000 82,000 194 1. 5 Yes very heavy. Bt 4 0. 77 128 7.1 7. 5 68 200 264 131, 000 207 1. 6 bo.

msm- 5 76 1 1.09 49 1.5 3.1 63 170 225 115, 000 87, 000 168 1. 3 D0. 2 0.86 98 3. 9 5. 4 63 197 240 93, 000 70, 000 214 1. 6 Do. Btms 3 0.154 49 10. 8 12. 3 63 187 282 113 018g No observation. 77 1 0. 965 135 5. 4 5. 4 58 177 245 e4, 000 94, 00o 211 gpni- Yes, very heavy.

ine 2 0.204 44 8. 3 8.3 58 220 280 14,000 32,000 69 Not apparent (t). 3 0. 139 0 0.0 0. 06 58 228 292 9, 400 25,000 5. 4 Do. 4 0.083 'lrace FEED COMPOSITION AND TREATMENT Composition, t weight Perce Resin Type Final S. P. Washing Procedure-Water: Approx. Batch Grav. lgfhgio 8 gal. per 45 gals. soln each wash Acldty' servent p Solids (Dimer) H10 (e) 73, 74, 75.-. 64. 2 33.8 2.0 0.802 55/45 (wt.)- 5 water, 0.6 weight percent dry 0 NAH CO3 +2 water. 76 45.5 43.7 10.8 0.84 55/45 (Wt.) 7Wiiter 7 77 61. 5 38.1 0.4 0.84 55/45 (Wt.) 6 Water 6 Noras (u) Based on 0.006 sq. ft. cross section.

(b) Based on 0.785 sq. it. cross section. 0 p. s. i. g. and coil outlet temp.; drum temp. actually lower since not steam jacketed.

(c) Based on 0.051 sq. ft. cross section. 0 p. s. i. g. and coil outlet temp.; drum is steam jacketed. (d) Discrepancies in heat transfer may in large part be explained by variations in H2O content oi' feed solution; see note (e).

(e) Samples taken may not be representative as regards H2O cont (j) Entrained resin issuing from vapor line believed to be material from run No. 1.

slowed up considerably during course of run No. 2.

PRODUCT QUALITY ent.

Flow of this material Loss, Sofmng weight 001er Cest iron Ash Gel percent Per cent Per cem Per cent 96 5. 1 12 Green 004 73 0. 90 94 3. l 11 34 2. 6 3. 2 11 02 01 66 7. 3 11 03 0. 2

The results above set out show the excellent quality of the polymer obtainable and the elflciency of operations of the procedure above described.

Thus the process of the invention polymerizes an olenic mixture, washes the mixture to substantial neutrality, dries the mixture and flashes it through a heated non-ferrous material coil to remove solvents in the shortest possible time with the least opportunity for the absorption of iron contaminants.

While there is above disclosed but a single embodiment of the process and product of the invention, it is possible to produce still other embodiments without departing from the inventive the appended claims as are stated therein or required by the prior art.

The invention claimed is:

1. In the processing of a, fusible eopolymeric resin, prepared from a mixture containing from 30% to 80% of a multi-olefin, having from 4 to 14 carbon atoms per molecule, and from 20% to of a mono-olen, having from 5 to 20 inclusive carbon atoms per molecule, by the application to the mixture of a Friedel-Crafts catalyst, at a temperature Within the range between +10 C. and 30 C., the steps in combination of diluting the polymerized mixture with warm, light naphtha to volatilize out unpolymerized material, washing the naphtha solution with mildly alkaline water solution with vfrom 3 to 11 washings; passing the naphtha solution over a heated metal surface containing less than 7% iron, at a critical speed and critical temperature indicated by a 40 `foot length .of 1 inch diameter pipe, at the temperature of 105 to 250 lbs. steam, at 'a speed of flow such that the polymer is in contact with the hot metal for a time interval not longer than 4 minutes.

2. In .the processing of a fusible copolymeric resin, prepared from a mixture .containing from 30% to 80% of a multi-olefin, having from 4 to 14 carbon atoms per molecule, and from 20% to 70% of .a mono-olen, having from 5 to Z0 inclusive carbon atoms per molecule, by the application to the mixture of a Friedel-Crafts catalyst, at -a temperature within the range between +l C. and 30 C., the steps in combination of diluting the .polymerized mixture with warm, light naphtha to volatilize out unpolymerized material, washing the naphtha solution with mildly alkaline water solution with from 3 to 11 washings; passing the naphtha solution over a heated metal surface containing less than 7% iron, at a critical speed and critical temperature indicated by a 40 foot length of 1 inch diameter pipe, at the temperature of 105 to 250 lbs. steam, at a speed of ow such that the polymer is in contact with the hot Ametal for a time interval not longer than l4 minutes, and carrying away volatile components by the-application to the hot resin material of a stream of super-heated steam.

3. In the processing of a fusible copolymeric resin, prepared from a mixture containing from 30% to 80% of a multi-olen, having from 4 to 14 carbon atoms per molecule, and from 20% to 70% of a mono-olen, having from 5 to 20 inclusive carbon atoms per molecule, by the application to the mixture of a Friedel-Crafts catalyst, at a temperature within the range between -|-l.0 C. and 30 C., the steps in combination of diluting the polymerized mixture with warm, light naphtha to volatiliae out unpolymerized material, washing the naphtha solution with mildly alkaline water solution with from 3 to 11 washings; passing the naphtha solution over a heated metal surface containing less than 7% iron, at a critical speed and critical temperature indicated by a 40 foot length of 1 inch diameter pipe, at the temperature of 105 to 250 lbs. steam at a speed of flow such that the polymer is in contact with the hot metal for a time interval not longer than 4 minutes, and thereafter collecting the resin in molten condition in a hot recever, composed of a metal containing less than 7% iron.

4. In the processing of a fusible copolymeric resin, prepared from a mixture containing from 30% to 80% 0f a multi-olefin, having from 4 to 14 carbon atoms per molecule, and from 20% to 70% of a mono-olefin, having from to 20 inclusive carbon atoms per molecule, by the application to the mixture of :a Friedel-Crafts catalyst, at a temperature within the range between +10 C. and 30 C., the steps in combination of diluting the polymerized mixture with warm, light naphtha to volatilize out unpolymerized material, `washing the naphtha solution with mildly alkaline water solution with from 3 to 11 washings; passing the naphtha solution over a heated metal surface containing less than 7% iron, at a critical speed and critical temperature indicated by a 40 foot length of 1 inch diameter pipe, at the temperature of 105 to 250 lbs. steam, yat a speed of flow such that the polymer is in contact Awith the hot metal for a time interval not longer than 4 minutes, and carrying away volatile components by the application to the hot resin material of a stream of super-heated steam, thereafter dis-'- charging the heated, steam treated resin into ra hot receiver, composed of a metal containing less than 7% iron, and treating it in the hot receiver with a further portion of super-heated steam.

5. In the processing of a fusible copolymeric resin, prepared from a mixture containing from 30% to 80% butadiene, and from 20% to 70% vdiisobutylene, by the 4application to the mixture of a Friedel-Crafts catalyst, at a temperature within the range between -|-l0 C. and 30 C., the steps in combination of diluting the polymerized mixture with warm, light naphtha to volatili'z out unpolymerized material, washing the naphtha solution with mildly alkaline water solution with from 3 to 11 washings; passing the naphtha solution over a heated metal surface containing less- Ythan 7% iron, at a critical speed and critical temperature indicated by a 40 foot length 'of 1 inch diameter pipe, at the temperature of to 250 lbs. steam, at a speed of ow such that the polymer is in contact `with the hot metal for' a time interval not longer than 4 minutes.

6. In the processing of 'a fusible copolymeric resin, prepared from a mixture containing from 30% to 80% of a multi-olefin', having from 4 to 14 carbon atoms per molecule, and from 210% to 70% of a mono-olefin, having from 5 to 20 inclusive carbon atoms per molecule, by the application to the mixture of a Friedel-Crafts catalyst at a temperature within the range between +10 C. and 30 C., the steps in combination of diluting the polymerized mixture with warm, light naphtha to volatilize out un-polymerized material, washing the naphtha solution with mildly alkaline Water solution with from i3 to 11 washings; passing the naphtha solution over a heated Monel metal surface containing less than 7% iron, at a critical speed and critical temperature indicated by a 40 foot length of 1 inch diameter pipe, at the temperature of 105 to 250 lbs. steam, at a speed of flow such that the polymer is in contact with the hot metal for a time interval not longer than 4 minutes.

7. In the processing of a fusible copolymeric resin, prepared from a mixture containing from 30% to 80% butadiene, and from 20% to 70% diisobutylene, by the application to the mixture of a Friedel-Crafts, at a temperature within the range between +10 C. and 30 C., the steps in combination of diluting the polymerized mixture with warm, light naphtha to volatilize out unpolymerized material, washing the naphtha solution with mildly alkaline water solution with from 3 to 11 Washings; passing the naphtha solution over :a heated Monel metal surface containing less than 7% iron, at a critical speed and critical temperature indicated by a 40 foot length of 1 inch diameter pipe, at the temperature of 105 to 25'0 lbs. steam, at a speed of flow such that the polymer is in contact with the hot metal for a time interval not longer than 4 minutes.

8. In the processing of a fusible copolymeric resin, prepared from a mixture containing from 30% to 80% of a multi-olefin, having from 4 to 14 carbon atoms per molecule, and from 20% to 70% of a mono-olefin, having from 5 to 20 inclusive carbon atoms per molecule, by the application to the mixture of a Friedel-Crafts catalyst, at a temperature Within the range between +10 C. and 30 C., the steps in combination of dil1 luting the polymerized mixture with warm, light naphtha to Volatilize out unpolymerized material, Washing the naphtha solution with mildly alkaline Water solution with from 3 to 11 washings; passing the naphtha solution over a heated nichrome alloy surface containing less than 7% iron, at a critical speed and critical temperature indicated by a 40 foot length of 1 inch diameter pipe, at the temperature of 105 to 250 lbs. steam, at a speed of ow such that the polymer is in contact with the hot metal for a time interval not longer than 4 minutes.

9. In the processing of a fusible copolymeric resin, prepared from a mixture containing from 30% to 80% butadiene, and from 20% to 70% diisobutylene, by the application to the mixture of a Friedel-Crafts catalyst, at a temperature Within the range between +10 C. and 30 C., the steps in combination of diluting the polymerized mixture with Warm, light naphtha to volatlize out unpolymerized material, Washing the naphtha solution with mildly alkaline water solution With from 3 to 11 washings; passing the naphtha solution over a heated nichrome alloy surface containing less than 7% iron, at a critical speed and critical temperature indicated by a 40 foot length of l inch diameter pipe, at the temperature of 105 to 250 lbs. steam, at a speed of flow such that the polymeris in contact with the hot metal for a time interval not longer than 4 minutes.

10. In the processing of a fusible copolymeric resin, prepared from a mixture containing from 12 30% to 80% isoprene, and from 20% to 70% pentene, by the application to the mixture of a Friedel-Crafts catalyst, at a temperature Within the range between +10 C. and 30 C., the steps in combination of diluting the polymerized mixture With Warm, light naphtha to Volatilize out unpolymerized material, washing the naphtha solution with mildly alkaline Water solution with from 3 to 11 washings; passing the naphtha solution over a heated Monel metal surface containing less than 7% iron, at a critical speed and critical temperature indicated by a foot length of 1 inch diameter pipe, at the temperature of to 250 lbs. steam, at a speed of oW such that the polymer is in contact with the hot metal for a time interval not longer than 4 minutes.

JOI-IN D. GARBER.

WILLIAM J. SPARKS.

DAVID W. YOUNG.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,982,708 Thomas Dec. 4, 1934 2,035,233 Hachwalt Mar. 24, 1936 2,297,722 Soday Oct. 6, 1942 2,297,723 Soday Oct. 6, 1942 2,297,724 Soday Oct. 6, 1942 2,374,242 Soday Apr. 24, 1945 

1. IN THE PROCESSING OF A FUSIBLE COPOLYMERIC RESIN, PREPARED FROM A MIXTURE CONTAINING FROM 30% TO 80% OF A MULTI-OLEFIN, HAVING FROM 4 TO 14 CARBON ATOMS PER MOLECULE, AND FROM 20% TO 70% OF A MONO-OLEFIN, HAVING FROM 5 TO 20 INCLUSIVE CARBON ATOMS PER MOLECULE, BY THE APPLICATION TO THE MIXTURE OF A FRIEDEL-CRAFTS CATALYST, AT A TEMPERATURE WITHIN THE RANGE BETWEEN +10* C. AND -30*C., THE STEPS IN COMBINATION OF DILUTING THE POLYMERIZED MIXTURE WITH WARM, LIGHT NAPTHA TO VOLATILIZE OUT UNPOLYMERIZED 